TWI221007B - Processing of semiconductor components with dense processing fluids and ultrasonic energy - Google Patents

Abstract

Method for processing an article with a dense processing fluid in a processing chamber while applying ultrasonic energy during processing. The dense fluid may be generated in a separate pressurization vessel and transferred to the processing chamber, or alternatively may be generated directly in the processing chamber. A processing agent may be added to the pressurization vessel, to the processing chamber, or to the dense fluid during transfer from the pressurization vessel to the processing chamber. The ultrasonic energy may be generated continuously at a constant frequency or at variable frequencies. Alternatively, the ultrasonic energy may be generated intermittently.

Description

1221007 Description of the invention: Technical field to which the invention belongs [_1] A small amount of pollutants is harmful to the manufacture of microchips for manufacturing semiconductor electronic components. Contaminants in the form of particles, films, or molecules can cause short circuits, open circuit stack errors, and other defects. These defects can cause the microelectronic circuit to fail σσ, and the failure will significantly reduce the yield and significantly increase the manufacturing cost. Prior art [002] Microelectronic circuit manufacturing requires many processing steps. The treatment is carried out under extremely clean conditions and the amount of contamination required to cause serious defects in the microcircuit is extremely small. For example, particles as small as 0.001 micron can cause serious defects in modern microcircuits. Microcontamination can occur at any time during the many steps required to complete a microcircuit. Therefore, wafers for microelectronic circuits need to be periodically cleaned to maintain economically efficient yields. Furthermore, it is necessary to closely control the purity and cleanliness of the processing materials. [0003] A variety of cleaning methods have been used in the manufacture of semiconductor electronic components. These methods involve immersion in liquid cleaning agents to remove contaminants by dissolution and chemical reactions. This latent immersion can also be used to reduce van der Waals adhesive force and introduce a double-layer repulsion force, thereby promoting insoluble particles to detach from the surface. The standard wet cleaning process commonly used starts with exposure to a mixture of sulfuric acid, hydrogen peroxide, and water ’at 110-130 ° C and then submerged in 20-25 ° C hydrofluoric acid or diluted hydrofluoric acid. Secondly, the particulates were removed with a mixture of ammonia, hydrogen peroxide and water at 60-80 ° C, and the metal contaminants were removed with a mixture of 60-20 (TC hydrogen chloride, hydrogen peroxide and water. After each step Washing with high purity water. The wet cleaning process encounters basic obstacles at sizes smaller than 0.10 microns. As the device geometry shrinks and the gate oxide thickness decreases, the removal of submicron particles gradually changes [0004] Diluted aqueous mixture containing sulfuric acid and hydrogen peroxide can be used to strip / remove the organic photoresist. Alternatively, a two-stage plasma or reactive ion halide process can be used, followed by the use of residual substances. Wet chemical cleaning for stripping / removing. Ozonized water has been used to decompose contaminates on the surface of carbides on silicon wafers. [0050] Some people have used a brushing method to apply liquid motion | Strive to improve the effect of the liquid submergence process on the contaminated surface. A typical application is to use a water cleaning device containing two facing brushes for scrubbing uprightly disposed in a place that can hold the process liquid. The wafer in the slot. [0006] The addition of ultrasonic energy can increase the effectiveness of the liquid submersion process. Sound waves with a frequency of more than 20,000 cycles per second (20KHz) (ie, exceeding the range of human hearing) have been used In order to transfer high-frequency energy to the liquid cleaning solution. [0007] When the size of the microelectronic circuit is reduced and the environmental restrictions are increased, the wet processing method may have problems. The limitations of the wet processing include the progressive pollution of the recycled liquid, From redeposition of contaminated chemicals, special disposal requirements, environmental damage, special safety procedures during handling, reduced effectiveness in deep patterned surfaces due to surface tension effects and pattern collapse (surface topography sensitivity), The effectiveness of cleaning depends on the surface wetting ability (to avoid re-adhesion of stains 7 1221007) and possible liquid residues that cause residual particles to adhere. Water-based cleaning agents based on chemical reactions with surface contaminants may also be present with New thin film materials or compatibility issues with more corrosive metals such as copper. In addition, International Technology R ad Qing f〇r

Semiconductors have proposed a 62% reduction in water use by 2005 and an 84% reduction in water use by 2014 to avoid water shortages. As wafer diameters continue to increase (with larger precision surface areas), larger amounts of liquid chemicals are required in the process. [0008] In view of these problems, a dry (anhydrous) surface cleaning method for semiconductor electronic components is being developed. Among these methods is a jet cleaning method for removing large particles from a dream wafer. However, air jets may not be effective for removing particles smaller than ^ microns in diameter, because the force holding the particles on the surface is proportional to the particle size 'and the aerodynamic head-on resistance generated by the flowing gas used to remove the particles is proportional to the square of the particle size . Therefore, as the particle size shrinks, the proportion of these forces tends to stick. In addition, the smaller particles are not exposed to the strong head-on resistance in the jet because they are usually located in the surface interface layer where the gas velocity is low. [_ 9] Although exposure to a combination of ozone and ultraviolet light can throw contaminated hydrocarbons on decomposition surfaces', this technology has not been effective in removing inorganic pollutants or particulates. Chen] Other alternative methods of wet cleaning include the use of air jets containing snow particles or pellets, where the snow particles or pellets are composed of frozen argon, nitrogen, water, or carbon dioxide and are used in " Sand blasting, contaminated watch In these two loading processes, the pressurized gas phase or gas / liquid mixture will expand to a pressure near or below atmospheric pressure in the nozzle 1221007. The resulting Joule-Thomson cooling (Joule -Thomson cooling) will form solid or liquid gaseous sol particles, and the solid or liquid gaseous sol particles will cross the interface layer and bombard the contaminated surface. This technology requires extremely clean and pure treatment shellfish. Feed into the gas Of small molecular contaminants (such as hydrocarbons) will condense in solid particles or droplets during expansion, causing new contaminants to deposit on the surface. Although these processes are useful for the removal of many surface contaminants, but It cannot remove all important contaminants present on the wafer surface, and has not been widely accepted by the semiconductor industry. [0011] Another submerged in supercritical fluids is wet cleaning Alternative methods. The effectiveness of supercritical fluids in a variety of cleaning and extraction applications has been well established and widely available in the literature. Supercritical fluids have a dissolving power much greater than the corresponding gaseous state, and can effectively dissolve and remove precision surfaces Excessive film and molecular pollutants. Reducing the pressure below the critical value can separate the pollutants from the cleaning agent, which can concentrate the pollutants for disposal, and enable the cleaning agent to be recycled and reused. [0 012] In particular, supercritical carbon dioxide has been used as a versatile and cost-effective method to overcome the problem of cleaning wafers before it is removed. Supercritical carbon dioxide can effectively clean smaller-sized parts and reduce the use of water, thereby increasing productivity It is also beneficial to the environment. Preliminary Cost of Ownership (Co0) research has confirmed that supercritical carbon dioxide cleaning is also more cost effective when compared to water-based washing. The carbon dioxide in the super-dagger state is particularly good. And has proven effective for removing organic impurities. It can be added with co-solvents or azeotropes 9 1221007 agent is modified to increase the range of pollutants removed, including particulates, primordial or chemical oxides, gold eyebrows, a-a impurities, and other inorganic materials. Ultrasonic energy can be added to the supercritical Fluid slag and Qin Yueyue reactors to improve the efficiency of the cleaning process. [0013] In the future, microcircuits will have smaller physical sizes and larger complexity, and will require more processing steps during manufacturing. Pollution control of process material systems and the processing environment will become even more important. Given these anticipated developments, 'improved wafer cleaning methods are needed to maintain or maintain these smaller and more complex microelectronic systems during manufacturing. Improve yield. In addition, smaller 幵 V body sizes and greater complexity will require improved process steps, including etching, thin film deposition, planarization, and photoresist development. The embodiments of the present invention are described below and are defined by the following patent claims, and it is an improved treatment method using a thick treatment fluid with ultrasonic energy. SUMMARY OF THE INVENTION [0014] A first embodiment of the present invention includes a method for processing an object, the method including: (a) entering the object into a sealable processing chamber, and sealing the processing chamber; (b) A thick fluid is prepared by: (M) entering a subcritical fluid into a pressurized container and isolating the container; and (b2) heating the subcritical fluid at a substantially fixed volume and a substantially fixed density to produce a thick fluid ; (C) conveying at least a portion of the thick fluid from the pressurized container to the processing chamber 122, wherein the conveyance of the thick fluid is driven by the pressure difference between the pressurized container and the processing chamber- To thereby pressurize the processing v cavity with the thick fluid being delivered; (d) input one or more processing agents into the processing cavity before (c) or during (c) or after (c), To provide a thick processing fluid; (e) inputting ultrasonic energy into the processing chamber, and contacting the object with the thick processing fluid to produce a waste thick processing fluid and a processed object; and (f) the waste thick The processing fluid is separated from the processed object. [0015] In (b2), a dense fluid may be generated in the pressurized container at a contrast temperature below about 1.8, where the contrast temperature is defined as the average absolute temperature of the thick fluid in the pressurized container after heating divided by The absolute critical temperature of the fluid. In (d), the object and the thick processing fluid may be brought into contact in the processing chamber at a comparative temperature between about 0.8 to about 1.8 in the processing chamber, where the comparative temperature is defined as The average absolute temperature of the thick processing fluid in the processing chamber during (d) is divided by the absolute critical temperature of the thick processing fluid. The thick fluid may contain one or more components selected from the group consisting of: carbon dioxide, nitrogen, methane, oxygen, ozone, argon, hydrogen, helium, ammonia, nitrogen oxide, thorium fluoride, Hydrogen chloride, sulphur trioxide, sulphur hexafluoride, nitrogen trifluoride, monofluoromethane, difluoromethane, trifluoromethane, trimethylacetate, tetra IL ethyl, pentafluoroethyl, perfluoropropane , Five I propane, six gas acetone, hexafluoropropylene, hexafluorobutadiene, and octafluorocyclobutane and tetrafluoro gas. The thick fluid may contain one or more hydrocarbons having 2 to 6 carbon atoms. 0 1 122 1007 dipropyl ether, methanol, ethanol, isopropanol, acetonitrile, ethanol, ethylene glycol, propylene glycol, ethylene glycol acetate [7] The total concentration of the one or more treating agents in the exposed treatment fluid may be between about 0.1 and 20% by weight. In an embodiment, the thick treatment fluid may include one or more treatment agents selected from the group consisting of: ethyl acetate, ethyl acetate, propyl acetate, butyl acetate, diethyl acetate, acrylic acid Nitrile, benzonitrile, cyanopropyl-mono-Sf * early acetate g, propane, butane, acetophenone, trifluoroacetophenone, triethylammonium, tripropylamine, tributylamine, 2,4 = Fluorenyl nitrogen benzene, difluorenylethanolamine, diethylethanolamine, diethylmethanolamine, difluorenylethanolamine, difluorenylamine, dimethylacetamide, ethylene glycol carbonate, carbonic acid Propylene ester, acetic acid, lactic acid, butanediol, propylene glycol, n-hexane, n-butane, hydrogen peroxide, third butyl hydrogen peroxide, ethylenediaminetetraacetic acid, catechol, bile test, and trifluoroacetic anhydride. [0018] In another embodiment, the thick treatment fluid may include one or more treatment agents selected from the group consisting of: hydrogen fluoride, hydrogen gasification, difluorinated gas, nitrogen difluoride, monofluoride Methane, difluoromethane, tris (methane), trifluoroethane, tetrafluoroethane, pentafluoroethane, perfluoropropane, pentafluoropropane, hexafluoroethane, hexafluoropropylene, hexafluorobutadiene, Octafluorocyclobutane, tetrafluoroethane, fluorotrifluoromethane (CF4〇), bis (difluorooxy) arsen (CF4〇2), melamine fluoride (C3F3N3), ethylene difluoride (C2F2N2), fluorene (CFO), carbon fluoride (CF20) and perfluoromethylamine (cf5N). [0 019] In yet another embodiment, the thick processing fluid may include one or more processing agents selected from the group consisting of: organometallic preform, photoresist, photoresist developer, intermediate Layer dielectric material, Shixiyan reagent and antifouling coating. 12 1221007 [0020] The pressure of the waste thick treatment fluid can be reduced to generate at least one fluid phase and one residual compound phase, and the phase can be separated to produce purified fluid and recover residual compounds. The purified fluid can be recycled to provide a portion of the subcritical fluid in (bl). The pressure of the purified fluid can be reduced to produce a further purified fluid phase and a new residual compound phase, and the phase can be separated to produce a further purified fluid and a new recovered residual compound. The further purified fluid can be recycled to provide a portion of the subcritical fluid in (bl). [0021] Prior to heating in (b2), the subcritical fluid in the pressurized container may include a vapor phase, a liquid phase, or a coexisting vapor and liquid phase. [0 022] Another embodiment of the present invention includes a method for processing an object. The method includes: (a) rotating the object into a sealable processing chamber, and sealing the processing chamber; (b) borrowing A thick treatment fluid is prepared by: (b 1) entering a subcritical fluid into a pressurized container and isolating the container; (b2) heating the subcritical fluid at a substantially fixed volume and a substantially fixed density to produce a thick fluid ; And (b3) inputting one or more treating agents into the pressurized container under the following conditions: before inputting the subcritical fluid into the pressurized container, or after inputting the subcritical fluid into the pressurized container; , But before heating the pressurized container, or after inputting the subcritical fluid into the pressurized container, and after heating the pressure container 13 121007; (c) removing at least a portion of the thick processing fluid from the pressurized container The pressure vessel is conveyed to the processing chamber, wherein the conveyance of the thick processing fluid is driven by the pressure difference between the pressure vessel and the processing chamber, thereby pressurizing the processing chamber with the thick processing fluid being conveyed; ( d) Supersonic The wave energy is input into the processing chamber, and the object is brought into contact with the transported thick processing fluid, thereby generating a waste thick processing fluid and a processed object; and (e) the waste thick processing fluid and the processed object Separation. [0 0 2 3] Another embodiment of the present invention includes an apparatus for processing an object. The apparatus includes: (a) a fluid storage tank containing a subcritical fluid; (b) one or more pressurized containers And a conduit mechanism for transferring the subcritical fluid from the fluid storage tank to one or more pressurized containers; (c) a heating mechanism for transferring each of the one or more at a substantially fixed volume and a substantially fixed density; The contents of the plurality of pressurized containers are heated to convert the subcritical fluid into a thick fluid; (d) a sealable processing chamber for contacting an object with the thick fluid; (e) an ultrasonic generation mechanism, It is used to input ultrasonic energy into the sealable processing chamber; (0) a catheter mechanism for transferring the thick fluid from the one or more pressurized containers into the sealable processing chamber; and (S ) — One or more treatment agent storage containers and pressurization mechanisms for injecting one or more treatment agents into (1) the one or more pressurized containers, 14 1221007 or (2) for the thick fluid Sent to the sealable processing chamber by the one or more pressurized container wheels The conduit mechanism, or (3) the sealable processing chamber. [0024] The device may further include a decompression mechanism and a phase separation mechanism to separate the waste thick processing fluid extracted from the processing chamber to produce At least one purified fluid and one or more recovered residual compounds. The apparatus may further include a circulation mechanism for circulating the purified fluid to the fluid storage tank. [0025] Another embodiment of the present invention relates to a method for A method for processing an object, the method includes: (a) entering the object into a sealable processing chamber, and sealing the processing chamber; (b) providing a thick processing fluid in the processing chamber; (c) when the object and When the thick processing fluid comes into contact, the ultrasonic energy is input into the processing chamber, and the frequency of the ultrasonic energy is changed to generate a waste thick processing fluid and a processed object; and (d) the waste thick processing fluid and the The processed objects are separated. During (c), the frequency of ultrasonic energy can be increased. Or, for example, the method of patent application scope No. 1 9 ii > t, soil ^ r,..., ^ ^ 1 y Where in (C ), The frequency of ultrasonic energy can be reduced. [0 0 2 6] The thick treatment fluid can be prepared in the following manner: (a) the subcritical fluid is input into a pressurized container and the container is isolated; (b) in essence Heating the subcritical fluid at a fixed volume and a substantially constant density to produce a thick fluid; and (c) providing the thick treatment fluid by one or more steps selected from the group consisting of 15 1221007: (1 ) When the thick fluid is sent from the pressurized container to the processing chamber, 'input one or more processing agents into the thick fluid; (2) input one or more processing agents into the pressurized container to form a thick processing fluid, And conveying the thick processing fluid from the pressurized container to the processing chamber; (3) after transferring the thick fluid from the pressurized container to the processing chamber, 'inputting one or more processing agents into the processing chamber in the processing chamber; Thick fluid; (4) before the sub-boundary fluid is input into the pressurized container, one or more treatment agents are input into the pressurized container; (5) after the sub-critical fluid is input into the pressurized container, but While heating the pressurized volume Before the treatment, one or more treatment agents are input into the pressurized container; (6) After the subcritical fluid is input into the pressurized container, and after heating the pressurized container, one or more treatment agents are input into the pressurized container. Pressure container. [0027] Alternatively, the thick processing fluid may be prepared in the following manner: (a) entering a subcritical fluid into the sealable processing chamber and isolating the processing chamber; (b) heating at a substantially fixed volume and a substantially fixed density The subcritical fluid to produce a thick fluid; and (c) providing the thick processing fluid by one or more steps selected from the group consisting of: 16 1221007 (1) the subcritical fluid is being input Before the sealable processing chamber, one or more processing agents are input into the sealable processing chamber; (2) after the subcritical fluid is input into the sealable processing chamber, but the subcritical fluid therein is heated Before, one or more processing agents are input into the sealable processing chamber; and (3) after the subcritical fluid is input into the sealable processing chamber, and after heating the subcritical fluid therein, one or A plurality of processing agents are input into the sealable processing chamber. [0028] In an alternative embodiment of the invention, the object may be processed in the following ways, the method comprising: (a) entering the object into a sealable processing chamber and sealing the processing chamber; (b) providing a thick fluid In the processing chamber; (c) when the object is in contact with the thick fluid, inputting ultrasonic energy into the processing chamber and changing the frequency of the ultrasonic energy to produce waste thick fluid and processed objects; and (d) Separate the waste thick fluid from the treated article. [0029] Another embodiment of the present invention may include a method for processing an object, the method includes: (a) entering the object into a sealable processing chamber, and sealing the processing chamber; 17 1221007 (b ) Providing a thick processing fluid in the processing chamber; (c) intermittently inputting ultrasonic energy into the processing chamber when the object is in contact with the thick processing fluid, thereby generating waste thick processing fluid and the processed object; and (d) separating the waste thick processing fluid from the processed article. [0030] In a further embodiment, a method for processing an object, the method includes: (a) entering the object into a sealable processing chamber, and sealing the processing chamber; (b) providing a slight fluid In the processing chamber; (c) when the object is in contact with the thick fluid, the ultrasonic energy is intermittently input into the processing chamber to generate waste thick fluid and the processed object; and (d) the waste thick The fluid is separated from the treated object. [0031] FIG. 1 is a density-temperature phase diagram of carbon dioxide. [0032] FIG. 2 is a general density-temperature phase diagram. [0033] FIG. 3 is a process flowchart of an embodiment of the present invention. [0034] FIG. 4 is a schematic view of a pressurized container used in the embodiment of FIG. 3. Embodiments [0035] The most frequently repeated step in the manufacture of integrated circuits is cleaning. In the design guidelines of 0. 18 microns, about 80 steps out of 400 total processing steps 18 1221007 steps are cleaning steps. Wafers are usually cleaned after each contaminating process step and before each warm operation to ensure circuit quality. Typical cleaning and removal applications include photoresist stripping / removal, post-mechanical planarization of particulates / residue removal (post-CMP cleaning), post-dielectric etching (or post-metal etching) particulates / residue Material removal and metal contamination. [0036] Various pollution-sensitive objects encountered in the manufacture of microelectronic devices and microelectromechanical devices can be cleaned or treated using embodiments of the present invention. The object may include components such as silicon or gallium arsenide wafers, gratings, photomasks, flat displays, inner surfaces of processing chambers, printed circuit boards, surface mount assemblies, electronics assemblies, sensitive wafer processing system components, optoelectronics Laser and aircraft hardware, surface micro-machining systems, and other related materials that are contaminated during manufacturing ^ ° In the cleaning process, typical pollutants removed by these objects can include organic pollution such as low and high molecular weight (Such as exposed photoresist: materials, photoresist residues, UV or x-ray hardened photoresist, fluorocarbon polymers and other organic and inorganic etching residues), ionic and neutral Light and heavy inorganic (metal) substances, water vapor, and insoluble materials containing flattened particles. The thick fluid is quite suitable for conveying the treatment agent to the processing steps (such as microelectronic components), and is suitable for removing the desired knife from the microelectronic components when the process steps are completed. These process steps are usually carried out in batches and can include, for example, cleaning, film peeling, finish, deposition, drying photoresist, and planarization. Other uses of the shrine fluid include the precipitation of nano particles and the suspension of metallic nano crystals. [038] A slight body is ideal for these applications, because these fluids 1221007 have essentially solvating power, low viscosity, high diffusion coefficient, and negligible surface tension (relative to the object being processed). As indicated earlier, the processing fluid used in microelectronic processing must be extremely pure, much higher purity than similar fluids used in other applications. The production of extremely high-purity thick fluids for these applications must be done with care, preferably using the methods described here. [0039] A single-component supercritical flow system is defined as a fluid located at its critical temperature and pressure. Relevant single & subfluids of the nature class ㈣ supercritical fluids are single-phase fluids whose temperature is lower than their critical temperature and whose pressure is higher than their liquid saturation pressure. In this disclosure +, the term "thick fluid" used for single-component fluids is defined as a single-phase fluid that contains both a supercritical fluid and a temperature below its critical temperature and a pressure above its saturation mobility. A fluid can also be defined as a single-phase fluid with a pressure higher than its critical pressure or a pressure higher than its liquid saturation pressure. The term "component," as used herein, means an element (such as hydrogen, helium, oxygen, nitrogen) or? Compounds (such as carbon dioxide, methyl gas, nitrogen oxides, sulfur hexafluoride). [0040] An early component subcritical flow system is defined as a fluid having a temperature below its critical temperature or a pressure below its critical pressure. [004U The thick fluid may be selected to include a mixture of two or more ingredients. In this case, a thick-flow system is defined as a single-phase multi-component fluid with a specific composition that is above its saturation or bubble point force, or a combination of pressure and temperature above the critical point of the mixture . The critical point of a multi-component fluid is defined as the combination of pressure and temperature where the fluid of a specific composition exists only in a single phase above the critical point. In this disclosure, the term "thick fluid" used for multi-component fluids is defined as a single-phase ㈣ that contains both the Transcendence 20 1221007 boundary fluid and a temperature below its critical temperature and a pressure above its bubble point or saturation migration force. ° Multi-component thick fluids can also be single-phase multi-component fluids with a volunteer force higher than their critical μ force or pressure higher than their bubble point or liquid saturation pressure. The difference between a multi-component thick fluid and a single-component thick fluid is that the critical mobility of liquid saturation history and the critical temperature are functions of the composition. As previously mentioned, the 'carcass' according to the present invention can be prepared from an initial subcritical fluid having a fixed density and composition.

[0042] A multi-component subcritical flow system is defined as a multi-component fluid having a specific composition, and the specific composition is located at or below its saturation or bubble point pressure or has a combination of pressure and temperature below the critical point of the mixture. [0043] The general definition of a thick fluid thus includes a single-component thick fluid as previously defined and a multi-component thick fluid as previously defined. Similarly, subcritical fluids can be single-component or multi-component fluids.

[0043] The definition of a single-component thick fluid is illustrated in the above figure, which is a representative carbon dioxide density-temperature phase diagram. The diagram shows a saturated liquid curve 1 and a fresh vapor curve 3, and the two ions are joined at a critical point 5 (critical temperature 87. "F and critical pressure un _). Isobaric lines (critical isobaric lines containing 1.071 psia) are shown therein. The line segments are for the dissolution curve. The area to the left of and surrounding the saturated liquid curve 1 and the saturated vapor curve 3 is a two-phase vapor-liquid region. The single-phase fluid region is outside the saturated liquid curve, the saturated vapor curve 3 and the dissolution curve 7, and to the right. The thick-flow system defined here is indicated by the slashed area 9. [0045] As shown in Figure 2, the general density-temperature graph can be defined by comparing temperature, contrast pressure, and contrast density. Contrast temperature (Tr) is defined as absolute 21 1221007 temperature divided by absolute critical temperature. Contrast force (ρ0 is defined as absolute migration force = absolute critical force. Contrast density (PR) is defined as density divided by critical existence. According to Definition, at the critical point, the contrast temperature and the density of the specific pressure are equal. Figure 2 shows similar features to Figure!, 1 includes a saturated liquid curve m and a saturated vapor curve 203, and the saturated liquid curve 2 i and the saturated vapor curve 203 are joined at a critical point 2 {) 5 (comparative temperature is 丄, contrast density is !, and contrast pressure is υ. Isobaric lines (including critical isobaric pressure of ㈣, line 207) are shown therein. On the left side of the saturated liquid curve 20m and the saturated vapour curve 2G3, the area surrounded by it is a two-phase vapor_liquid :. The diagonal line above the PR = 1 isobaric line and to the right of the Tr = 1 critical temperature is single. Phase compression liquid region. The dense fluid defined here includes both a single-phase supercritical fluid region 209 and a single-phase compressed liquid region 211. [0046] The formation system of the thick fluid in the embodiment of the present invention is illustrated in FIG. 2 as an example. In the-embodiment, the point a And the liquid are input into the container and sealed therein. The sealed container is heated in an equal volume (that is, a substantially fixed volume) and an equal density (that is, a substantially fixed density). The fluid moves along the line segment to point a , And a supercritical fluid is formed in the region 209. Alternatively, the fluid at point a can be heated to a temperature lower than the critical temperature (Tr = 丨) to form a compressed liquid. This is also a universal thick as previously defined Fluid. In another embodiment, the two-phase vapor-liquid mixture at point b is input into a container and sealed therein. The sealed container is of equal volume (ie, substantially fixed volume) and constant density (ie, substantially fixed density). ). The fluid moves along the line segment shown to point b, and a supercritical fluid is formed in region 9. This is a general-purpose thick fluid as previously defined. In another embodiment, 22,122,007, the system The saturated vapor at point c is introduced into the container and sealed therein. The sealed container is heated in an equal volume (that is, a substantially fixed volume) and an equal density (that is, a substantially solid density). Move to the point along the line segment shown, and a supercritical fluid is formed in the region 2G9. This is a universal thick fluid as previously defined. [0047] The final density of the thick fluid depends on the volume of the container and the initial input of the container 7 Relative quantity of vapor and liquid. Therefore, a wide range of densities can be obtained by this method. The terms "substantially fixed volume," and "substantially fixed density" mean that density and volume remain fixed (except when the container is heated, (Other than negligible minor changes that may occur). [0048] The thick fluids actually used in the present invention may be single-component fluids or multi-component fluids, and may have a contrast temperature in the range of about 0.8 to about 18. In The comparative temperature is defined as the absolute temperature of the fluid divided by the absolute critical temperature of the fluid. [0049] The thick fluid may include, but is not limited to, one or more components selected from the group consisting of: carbon dioxide, nitrogen, methyl alcohol, oxygen, ozone, argon, hydrogen, helium, 4, nitrogen oxide Hydrocarbons with 2 to 6 carbon atoms, hydrogen fluoride, hydrogen chloride, sulfur trioxide, sulfur hexafluoride, nitrogen trifluoride, chlorine trifluoride, monofluoromethane, difluoromethane, trifluoromethane, trifluoromethane Fluoroethane, tetrafluoroethane, pentafluoroethane, perfluoropropane, pentafluoropropane, hexafluoroethane, hexafluoropropylene, hexafluorobutadiene, and octafluorocyclobutane and tetrafluoromethane. [0050] A thick process stream system is defined as a thick fluid to which one or more processing agents have been added. A treatment agent is defined as a compound or combination of compounds that causes physical and / or chemical changes to occur on an object or substrate that is in contact with a thick processing fluid. The treating agent may include, for example, a film release agent, a cleaning or drying agent, an azeotropic agent, an etching or planarizing reactant, a photoresist developer, and a deposition material or reactant. The total concentration of these treatment agents in the thick treatment fluid is typically less than about 50% by weight and can be in the range of 0.1 to 20% by weight. After the treatment agent is added to the thick fluid, the thick treatment fluid generally remains single-phase. Alternatively, the thick treatment fluid may be an emulsion or suspension having a second suspended or dispersed phase containing a treatment agent. Thick processing fluids can be used for applications such as film peeling, cleaning, drying, etching, planarization, deposition, extraction, photoresist development, or suspension nanoparticle and nanocrystal formation. [0051] As used herein, the term "treated" or "treated" means contacting an object with a thick fluid or thick processing fluid to cause a physical and / or chemical change to the object. The term " Article, means any article that can come into contact with a thick fluid or a thick processing fluid. Representative objects can include, for example, silicon or gallium arsenide wafers, gratings, photomasks, flat-panel displays, inner surfaces of processing chambers, printed circuit boards, surface mount assemblies, electronic assemblies, and sensitive wafer processing systems Components, optoelectronics, laser and aircraft hardware, surface micromachining systems, and other related items that were contaminated during manufacturing. The term "processing" may include, for example, film peeling, cleaning, drying, etching, planarization, deposition, stroke, photoresist, or nanoparticle formation with nanocrystals. [0050] Embodiments of the present invention can be illustrated by making and using thick processing fluids for cleaning or processing objects such as microelectronic components. The typical process of this embodiment is shown in FIG. 3, which illustrates an isovolumetric carbon dioxide pressurization system for generating a carbon monoxide thick fluid of 24 1221007 (the carbon dioxide thick fluid is used for ultrasonic electronic component cleaning chambers or processing equipment), and It contains a carbon dioxide recovery system for the separation of pollutants in the extraction | 'circulating carbon dioxide. The liquid carbon dioxide and its equilibrium vapor are usually stored in a carbon dioxide supply container 301 at room temperature; and the vapor pressure of carbon dioxide is, for example, 70 ° F, at 854 psia. At least one carbon dioxide pressurized container is placed at the outlet end of the supply trough 301. In this embodiment, the three pressurized containers 303, 305, 309 (which will be described in more detail below) are respectively passed through the manifold 3H and the lines 313, 315, and 317 to communicate with the carbon dioxide supply container 301. . These lines are equipped with valves 319, 321, 323, respectively, to control the flow of carbon dioxide supplied from the supply container 301 to the pressurized container. The fluid supply lines 325, 327, and 329 are connected to the manifold 331 through valves 333, 335, and 337, respectively. [0053] The pressurized container 303 is illustrated in detail in FIG. 4. The pressurized container 303 includes an outer pressure envelope 401, an inner container 403, and a thermal insulator 405 interposed between the inner container and the outer pressure envelope. A preferred method is to minimize the thermal mass of the inner container 403 to reduce the cooling time when the container is just filled with the carbon dioxide supply container 301. The inner container 403 passes through the opening 407 and communicates with the thermal insulator 405 to ensure that the pressure inside and outside the inner container 403 is almost equal. This will reduce the wall thickness and thermal mass of the inner container 403. The opening 4 0 7 may contain a defogging medium such as a metal mesh or a porous sintered metal (not shown in the drawing) to prevent liquid carbon dioxide droplets from migrating into the thermal insulator 405. [0054] The liquid level in the pressurized container can be controlled by a pressure difference sensor 4009, which is controlled by the pressure difference sensor 4009. The pressure sensor 4 passes through the pipelines 411, 413, 415 and the inner valley device 403. Internal phase circulation. A typical liquid level appears between liquid 417 and vapor 419 in the inner container 403. The inner container 403 communicates with the lines 313 and 325 in FIG. 3 through the line 420. [0055] Heat can be supplied to the inner container 403 by any desired method. In one embodiment, the hot heating fluid 421 is supplied through a line 423 to a heat exchanger 425, and the heat exchanger 425 heats the liquid 417 and the vapor 419 by indirect heat exchange. The cooled heated flow system is discharged through line 427. The heat exchanger 425 may be any form of heat exchange assembly. A useful heat exchanger is always a tube body with longitudinal fins as shown, in which several fins 429 are brazed or welded to the tube body 431. The temperature and flow rate of the heating body 421 can be adjusted to control the heating rate during pressurization and the final temperature and pressure of the thick fluid formed in the inner container 403. [0056] Returning now to FIG. 3, the carbon dioxide supply container passes through the bidirectional flow pipe 339 and is connected to the dilute carbon liquefier 341 located above the carbon dioxide supply container 301. The heat exchanger 343 is used for cooling the inner part of the liquefier 341. The heat exchanger 343 may be a flat plate and a heat sink, or other types of heat exchangers (such as the heat exchanger 425 in FIG. 4). The cooling flow system is supplied through line 330 and may be cooling water such as room temperature; this can maintain the pressure in the carbon monoxide supply container 301 at a corresponding carbon monoxide vapor pressure. [0057] In the example, the valve 319 is open and the valve is closed. The valve 335 or 337 can be opened to pressurize the container 309 or 309 t, the thick body of carbon monoxide to the manifold 331 丨 where the pressurized container 3505 26 1221007 or 309 can be pre-loaded with carbon dioxide and proceed in the following manner Pressurize. The liquid carbon dioxide passes through the manifold 311, the valve 319, and the line 313 and flows downward from the supply container 301 into the pressurized container 303. When liquid carbon dioxide enters a pressurized container 3 03 that has been warmed in the previous cycle, an initial liquid vaporization will occur. When the liquid flows downward into the pressurized container 303, the warm, sudden base gas passes through the line 313 and the manifold 311 and returns upward to the carbon dioxide supply container 301. Warm flash steam returns to the carbon dioxide supply vessel and increases the pressure therein. The excess vapor passes through the line 339 and flows from the supply container 301 to the carbon dioxide liquefier 341. The vapor cools and condenses, and passes through the line 339 and flows down to the supply container 301. [0058] After preliminary cooling and pressurization, liquid carbon dioxide flows from the supply container 301 into the pressurized container 303. When the pressurized container is loaded with the desired depth of liquid carbon dioxide, the valve 319 is closed to isolate the container. The carbon dioxide isolated in the container 303 is heated by the previously disclosed indirect heat transfer method, and is pressurized as the temperature increases. The pressure is monitored with a pressure sensor 345 (pressure sensors 347, 349 are used in a similar manner for containers 305, 309, respectively). When heat is transferred to the carbon dioxide in the container 303, the temperature and pressure rise, and the separated liquid and vapor phases become a single phase to form a thick fluid. This thick fluid can be further heated to become a supercritical fluid (a supercritical fluid is defined as a fluid whose temperature is above the critical temperature and whose pressure is above the critical pressure). In contrast, a subcritical flow system is defined as a fluid whose temperature is below a critical temperature or whose pressure is below a critical pressure. The carbon dioxide loaded into the pressurized container 303 before heating was a subcritical fluid. The subcritical fluid can be a saturated vapor phase, a saturated liquid, or a two-phase fluid with coexisting vapor and liquid phases. 27 [_9] When more heat is transferred, the temperature and pressure rapidly rise to supercritical levels, and a supercritical fluid with a desired density is formed. The final carbon dioxide pressure in a known volume of the valleyr can be estimated from the initial liquid loading. For example, at 854 psi ^ 7 (rF, the density of liquid carbon dioxide in the vessel is 47.61b / ft3, and the density of the coexisting carbon dioxide vapor is 13 3 b / ft. If the liquid carbon dioxide occupies 46.3% of the container volume, the carbon dioxide Vapor occupies the remaining 53.7% volume. In this example, the average density of all carbon dioxide in the container can be calculated as 0.463 (47 6 (13 · 3) or 29 · 2 lb / ft3. * 37 [_〇 ] Because the internal volume of the container and the mass of carbon dioxide in the container remained substantially unchanged during the heating step, the flatness of the loaded carbon dioxide remained essentially unchanged at 29.2 lb / ft3 (with temperature It has nothing to do with pressure.) In this example, heating the selected initial carbon dioxide carrier at a constant density of 29.2 lb / ft3 in a constant volume (fixed volume) will pass through a critical temperature of 87 · 9T and a critical pressure. Is the critical point of 071 psia. More heat will form a supercritical fluid with a fixed density of 29.2 lb / ft3 at the temperature and pressure. A lower density supercritical fluid will be formed when the initial amount of carbon dioxide in the container is small. Critical fluid In contrast, when the initial amount of liquid carbon dioxide in the container is large, a higher density supercritical fluid will be formed. The pressure generated by heating a higher density supercritical fluid to a specific temperature is higher than heating a lower density supercritical fluid to The pressure generated at the same temperature is south. [0061] The highest theoretical pressure can be obtained when the pressurized container is completely filled with liquid carbon dioxide from the beginning without leaving a vapor gap in the container. For example, 28 1221007 at 70 ° At F, the average density of the saturated carbon dioxide liquid in the container is 47 · 6 · lb / ft3. The initial heating of the liquid carbon dioxide will transform the saturated liquid into a thick fluid in the phase diagram area, sometimes called a compressed liquid or a supercooled liquid When the fluid is heated to a critical temperature above 87 · 9 F, it becomes a defined supercritical fluid. In this example, carbon dioxide can be heated to a temperature of 189 F at a fixed density of 47 · 6 lb / ft3, at about A supercritical fluid is generated at a pressure of 5, 000 pSia. [0 0 6 2] By using the method exemplified in the previous example, a thick solution can be prepared at any selected density, temperature and pressure. Fluid. When the composition is fixed, only two of the two parameters are independent; the better and most convenient way to prepare a thick fluid is to choose the initial loading density and composition in the pressurized container, and then The carrier is heated to the desired temperature. Proper selection of the initial carrier density and composition will produce the desired final pressure. [00 63] When carbon dioxide is used as the single-component thick processing fluid, carbon dioxide can be heated to about 100T to about A temperature between 500 ° C to produce a lonely thick fluid pressure in a pressurized container. More generally, when any component or component is used as a thick fluid, the fluid in the pressurized container can be heated to a contrast temperature of up to about 1.8; where the contrast temperature is defined as the pressure in the pressurized container The average absolute temperature of the fluid after heating is divided by the absolute critical temperature of the fluid. For fluids containing any number of components, the critical temperature is defined as the temperature at which a fluid always exists as a single-fluid phase at a temperature below / m degrees south. [0064] Returning now to FIG. 3, the valve 333 is opened, and under the control of the flow of the metering valve 351, the thick fluid prepared by the front peeling is passed through the manifold 331. As required, 29 1221007 can be used by pumps 357, 359 to transfer one or more associative agents or treatment agents from the azeotrope 刎 storage troughs 353, 355 to the thick fluid in line 361 to improve the t, thick treatment fluid (In cleaning applications it can be called thick cleaning fluid). The thick processing fluid is fed into a sealable processing chamber or process equipment 362 containing one or more objects 363 to be cleaned or processed, and the valve 333 is closed. These items are passed through the door, sealed (not shown in the drawings) and placed in advance on a carrier 365 in the process equipment 362. The temperature in the process equipment 362 is controlled by a temperature control system 367. The fluid agitation system 369 performs mixing in the process equipment 362 to promote contact between the thick processing fluid and the object. [0065] The processing chamber or process equipment 362 is equipped with an ultrasonic generator 37, which is an array of ultrasonic transmitters connected to a high-frequency power source 371. The ultrasound transmitter can be any commercially available unit, such as Morgan, UK

Ultrasonic speakers from Electro Ceramics of Southampton. The ultrasonic generator 370 can generally operate in the frequency range of 20 KHz to 2 MHz. In this disclosure, the term "ultrasonic" means any fluctuation or oscillation with a frequency above the human hearing limit (about 2Ό Kflz). The high-frequency power source 371 typically provides about 20 W / in2 to about 40 W / in2 ultrasonic power Power in the density range. During the cleaning step, the inside of the process equipment 362 is typically exposed to ultrasound for 30 to 120 seconds. [0066] The ultrasound transmitter can be constructed of a piezoelectric or magnetostrictive structure. The piezoelectric transmitter contains an application Crystals that oscillate at ultrasonic frequencies when alternating current is applied. Durable magnetostrictive transmitters consist of coiled iron or nickel sheets. The transmitter is usually built into a "sensor" assembly, and the sensor assembly Includes sonic booster and Laba (not shown in the figure). The transducer 1221007 can be used to enhance the power of input fluid, pressure vessel wall or substrate carrier. [〇〇67] Ultrasonic transmitter array 37 〇 It can be installed horizontally on the processing object · facing and facing it (shown in Figure 3), so that the sound wave is generated in the downward direction. Upward and directly impact the object 363. Alternatively, the transmitter array can be uprightMounted on either side of the cleaning object (not shown in the drawings) so that the ultrasonic waves are generated in a horizontal direction across the cleaning object. [0068] In another alternative, the transmitter array can be mounted horizontally Beneath and in contact with the vehicle 365 (not shown in the drawing) so that the ultrasonic waves are generated in an upright direction and penetrate the vehicle 365 upwards. This structure can be used, for example, to apply the maximum ultrasonic energy to Wafer surface, especially when chemical reactions such as film deposition, etching, or electropolishing occur on the wafer surface. The circle can be positioned in any orientation, that is, up, down, or sideways. In this state, the sound waves The flow will bring the reaction products and pollutants off the surface. The sonic flow enters from the side and leaves the surface. The dissolved materials and suspended particles tend to leave the area where the sonic energy is concentrated, and this configuration will bring the concentrated material away from the surface. [0069] Although the ultrasonic transmitter array ultrasonic generator shown in Figure 3 · 370 is installed in the process equipment 362, it can be optionally installed in the manufacturing equipment 362. The surface _L 'of the equipment container so that the generated acoustic wave energy penetrates the container wall surface. [0070] The initial pressure in the pressurized container 303 and the temperature in the process equipment 362 can be selected so that whether azeotrope is added or not Agent or other treatment agent in the original thick fluid 'The thick cleaning fluid in the process equipment 362 is usually still a single-phase thick fluid as defined before the delivery step. Alternatively, the thick treatment fluid may be 31 1221007 Emulsions or suspensions of two suspended or dispersed phases

[0071] A variety of pollution-sensitive objects are encountered in the manufacture of microelectronic devices, and these microelectromechanical devices can be cleaned or treated using the present invention. The object may include, for example, silicon or gallium arsenide wafers, gratings, photomasks, flat displays, inner surfaces of processing chambers, printed circuit boards, surface adhesion assemblies, electronic assembly sensitive wafer processing system components, optoelectronics, Laser and aircraft hardware, surface micromachining systems, and other related items that were contaminated during manufacturing. Typical contaminants removed by these objects during the cleaning process may include organic pollutants such as low and high molecular weights (such as exposed photoresist materials, photoresist residues, external light or X-rays Hardened photoresist, carbon-containing polyσ and other organic and inorganic residuals), compounds containing ionic and non-ionic inorganic metals, water vapor, and insoluble materials containing flattened particles after

[0072] The sealed process equipment can be pressurized to a supercritical pressure of 1,100 () to 1 (), such as 3, preferably 15 () () to (7, 5) psia. This equipment usually operates at a supercritical temperature of up to 5 Saki, and can operate in the range of 100 F to 200 F. The temperature in process equipment 362 is controlled by a temperature control system 367. Usually, at The contact between the object 363 and the washing fluid in the process equipment 流体 can be above 1.G and usually between about 1. 8; black; ^ + & the degree is formed, where the comparison temperature is defined as cleaning The average absolute temperature of the internal fluid is divided by the absolute critical temperature of the fluid. [0073] There are several feasible alternative forces for feeding the co-foaming agent or treatment agent into the pipeline 361 to mix it with the thick fluid before it enters the process equipment 362. In an alternative, the thick fluid can be loaded into the process equipment 362 before the thick fluid is loaded into the pressurized container 303/32 1221007 equipment. In another alternative, the dense fluid can be loaded into the equipment After that, the azeotrope is directly input into the process preparation 362. In yet another alternative In addition, the azeotrope can be directly input into the pressurized container 303 before it is loaded into the pressurized container 303 by the supply container. In a further alternative, the pressurized container can be loaded with pressure in the pressurized container 303. After the container 303, but before the pressurized container 303 is heated, the azeotrope is directly input into the pressurized container 303. In the final alternative, the supply container 301 can be loaded into the pressurized container 303 After heating the pressurized container 303, the azeotrope is directly input into the pressurized container 303. Any of these alternatives can be completed using the appropriate pipelines, manifolds and valves in Figure 3. [0074 ] In addition to the strong stirring provided by the ultrasonic transmitter 37, the inside of the process equipment 362 can be mixed by a fluid stirring system 369 to increase the contact between the thick cleaning fluid and the object 363. The pump 372 and the filter 373 can be used The formed circulating fluid system provides additional fluid agitation. The filter 373 is used to remove particulate pollutants from the circulating fluid; the fluid agitation produced by increasing the convective motion of the fluid will mix thick fluids and promote pollutants or reactions Produce [0075] When the cleaning cycle is completed, the valves 375, 377 are opened to depressurize the process equipment 362, thereby allowing the contaminated thick fluid to flow through the heat exchanger gw and cool its temperature. To 70T to 150 Torr. The reduction of pressure and temperature will cause the pollutants and azeotrope dissolved in the thick fluid to condense, and the fluid containing suspended pollutants and azeotrope will flow through line 381 and enter the separator 383. The condensed pollutants and azeotrope are removed via line 385, and the purified fluid passes through line 387 to the intermediate fluid storage container 389. The pressure in the storage container 389 is between the supercritical extraction pressure in the process equipment 362 and the pressure in the carbon dioxide supply container 301. Generally, the pressure of the process equipment 3 62 is reduced to 9 q 0 to 1,100 psia 0 [0 076] during the decompression step, and the valve 333 can be opened as needed to make the pressure The carbon dioxide of the threshing device 3 0 3 also flows through the cooler 379 and the separator 383 together with the contaminated decompressed fluid. After the initial decompression of the process equipment 362, the carbon dioxide from the pressurized container 303 can be used for part of the pressurization and strip washing process a and 3 2 2 to dilute and remove residual pollutants and azeotrope; Cooler 379 and separator 383 depressurize the process equipment to a pressure of 900 to 1,100 psia. After the valves 375 and 377 are closed, the residual carbon dioxide in the process equipment 3 62 is discharged through the valve 3 91 to reduce the pressure to atmospheric pressure. Second, the process equipment 362 can be vented to sub-atmospheric pressure as needed. At this time, the sealable inlet (not shown in the drawing) of the process equipment 362 is opened, the processed objects are removed, and another set of contaminated objects is placed for the next cleaning cycle. [0077] Another cooler and separator similar to the cooler 379 and the separator 383 can be installed on the line 3 8 7 if necessary. The use of the second stage separation at intermediate pressure can more effectively separate the contaminants and azeotrope from the carbon dioxide solvent 'and allow some degree of fractionation between the pollutants and the azeotrope. [0078] The carbon dioxide in the intermediate fluid storage container 389 typically has a pressure in the range of 900 to 1,100 psia and can be filtered by the filter system 393 before being recycled to the liquefier 341 via lines 395,397; 34 1221007 The carbon dioxide is liquefied in the liquefier 341 and returned to the carbon dioxide supply trough 301 'for reuse. The supplemental carbon dioxide in the form of a vapor or liquid can be directly added (not shown in the figure) to the carbon dioxide supply container 301 through a line 398 and a valve 399. [0079] Alternatively, the purified carbon dioxide in line 38? Or line 395 can be directly discharged to the atmosphere (not shown in the figure) without a front-recovery cycle. In this embodiment, the carbon dioxide is input through the line 398 and the valve 399, and the non-circulation mode is used. [0080] A plurality of pressurized containers can be used in a typical process of a previous release. For example, when the pressurized container 3 in FIG. 3 is filled and heated, the pressurized container 305 (filled and heated in advance to provide a thick fluid under the desired conditions) can be passed through the line 327, the valve 335, The manifold 331 and the pipeline 361 supply the process equipment 362. It can be expected that three pressurized containers 303, 305, and 307 operate in a staggered cycle. One of them supplies a thick fluid to the process equipment 362, the other is filled with carbon dioxide by a carbon dioxide supply container 3101, and the second is filled with After heating. Using a plurality of pressurized containers in this manner increases the productivity of the process equipment 362 and allows for a spare waste container when a pressurized container is taken offline for maintenance. [0081] Although the previously disclosed typical process uses carbon dioxide as a thick fluid, other thick fluid components may be used for appropriate applications. The thick fluid may contain one or more ingredients selected from the group consisting of: di-emulsified stone, gas, scorching, oxygen, ozone, argon, hydrogen, helium, ammonia, oxidation, and having 2 to 6 carbons. Atomic hydrocarbons, hydrogen fluoride, hydrogen chloride, sulfur trioxide, sulfur hexafluoride, nitrogen trifluoride, trifluoride gas, and fluorocarbons; of which 35 1221007 the fluorocarbons include compounds such as (but not limited to) Fluoroethane, difluoromethane, 'trifluoroethane', tetramethane, pentoxane, over-propane, pentafluoropropane, hexafluoroethane, hexafluoropropylene (Gh), hexafluorobutadiene ( C4Fe) and octafluorocyclobutane (c'F8) and tetrafluorochloroethane. [0082] A thick processing fluid is generally defined as a thick fluid to which one or more processing agents have been added. A treatment agent is defined as a compound or combination of compounds that causes physical and / or chemical changes to an object or substrate that is in contact with a thick processing fluid. The treating agent may include, for example, a film release agent, a cleaning or drying agent, an azeotropic agent, an etching or planarizing reactant, a photoresist developer, and a deposition material or reactant. The total concentration of these treatment agents in the thick treatment fluid is typically less than about 50% by weight, and can be in the range of 0.1 to 20% by weight. After the treatment agent is added to the thick fluid, the thick treatment fluid typically remains single-phase. Alternatively, the thick treatment fluid may be an emulsion or suspension having a second suspended or dispersed phase containing a treatment agent. [0083] A typical process previously described with reference to FIG. 3 may use one or more azeotropic agents to be mixed with the thick fluid to provide a thick film peeling or cleaning fluid containing from 0.1 to 20% by weight azeotrope. An azeotrope is defined as a treatment agent used to increase the cleaning ability of a thick fluid to remove contaminants from a contaminated part. An azeotropic agent may generally include solvents, surfactants, clamp agents, and chemical modifiers. Some representative examples of azeotropic agents include acetylene alcohols and dienzymes, organosilanes, ethyl acetate, ethyl lactate, propyl acetate, butyl acetate, diethyl ether, dipropyl ether, methanol, ethanol, Isopropanol, acetonitrile, propionitrile, styronitrile, cyanoethanol, ethylene glycol, propylene glycol, ethylene glycol acetate, malonate monoacetate, acetone, methyl ethyl ketone, acetophenone, trifluorophenylethyl Ketone, tri 36 1221007 month female, tripropylamine, tributylamine, 2, 4 difluorenyl nitrogen benzene, dimethylethanolamine, diethylethanolamine, diethylmethanolamine, dimethylmethanolamine, diamine Methylformamide, dimethylacetamide, ethylene glycol carbonate, propylene carbonate, acetolactone I, butanediol, propylene glycol, n-hexane, n-butane, hydrogen peroxide, third butyl peroxide Hydrogen oxide, and such as ethylenediaminetetraacetic acid (EDTA), catechol, choline, cold diketone and cold ketoamine ligands, trifluoroacetic anhydride (tfaa), citric acid, iS glycol And halogenated alkane is hydroxy. [0084] The thick processing fluid prepared and processed by the method of the present invention can be used in other processing steps in the manufacture of electronic components, including: removing material from a part (etching, drying and planarizing), depositing the material on On a part (film deposition), or chemical modification of the material on a part (photoresist development). [0085] Surface etching is a chemical reaction process, which is usually performed using a liquid mixture or a dry electropolymerization process. This process is used to reduce the thickness of the surface of the conductive substrate, remove excess thin layers such as surface oxides, and form surface features such as channels or vias. The surface treatment can be performed in a dense phase fluid system using ultrasonic enhancement. [0086] Ultrasound can be used to increase the reaction rate of thin metal film deposition. The thin film is usually deposited from a metal preform, and the metal preform system is subjected to a reduction reaction on a heated surface using a reducing agent such as hydrogen. Using ultrasonic energy in thick processing fluids will increase the reaction rate, thereby improving process efficiency and film quality. [0087] Photoresist development is usually performed in a liquid phase system using a chemical such as tetramethylammonium hydroxide (TMAH) to expose the exposed photoresist to 37 1221007 d. This process can be performed in a dense phase fluid system according to the present invention using ultrasonic energy to increase the surface chemical development of the photoresist. The application of ultrasonic energy in the thick-phase processing fluid can increase the diffusion of chemical reactants and reaction products near the surface of the processing object. [0080] In these alternative processing steps, a suitable processing agent or reactive alpha may be added to the thick fluid to form a thick processing fluid. Some representative reactive compounds that can be added to thick fluids as processing agents for etching or planarization processes may include, for example, hydrogen fluoride, hydrogen gas, hexafluoroethane, nitrogen trifluoride, reactive polishing compounds, etc. Slurry (containing alumina, silica, hafnium oxide, or magnesium abrasive particles suspended in acid or alkali (ie, potassium hydroxide or ammonia-containing mixture), and an electrolytic solution for back-plating metal surfaces. Some representative reactive and non-reactive compounds that can be used to deposit thick fluids used in the deposition process may include, for example, organometallic preforms, photoresists, photoresist developers, interlayer dielectric materials, Silane reagent and various coating materials (including but not limited to antifouling coating). Representative reactive compounds that can be added to thick fluids used in photoresist development include tetramethylammonium hydroxide (TMAH). Methanol is a representative compound that can be added to thickening fluids used in drying processes. In these alternative uses of thick processing fluids, to be suitable for these alternative applications, the process equipment 362 previously shown for cleaning in Figure 3 may be replaced with a suitable process equipment. [0089] The present invention combines ultrasonic energy with latent immersion of a thick fluid in the same processing equipment at the same time. Therefore, the processed semiconductor substrate or object is exposed to an intensive thick fluid treatment that contains both dissolution and / or chemical reactions and process ultrasonic energy enhancement. The previously announced fluid agitation auxiliary mechanism (ie, the flow 38 1 ^ 1007 body stirring system 369 and the circulating fluid system consisting of $ q79 life, accounting, and circulator 373) can also be used to strengthen the ultrasonic wave. In this way, the solvent or treatment agent in the process can penetrate into a fairly thick pollutant film (such as photoresist)) and the inert insoluble residue is caused by the fluid phase shock = + money effect and sonic flow Q / Month 冼 / induced flow in the body). [_〇] Increasing the rate of penetration of the solvent thin film by the ultrasonic energy is helpful for the cleaning of semiconductor substrates'. In the application of semiconductor substrate cleaning, high productivity is necessary to provide an economical process. Ultrasonic mixing also increases the uniformity of the cleaning process, so it can achieve better cleaning or surface treatment performance than using submerged immersion of thick fluid alone. [0090] Ultrasonic energy can generate local pressure fluctuations in thick fluids or thick processing fluids, which is helpful for cleaning or processing performance. The pressure pulse formed by the ultrasonic wave will cause the dense fluid density to fluctuate correspondingly to the mean value, which will then cause the fluid solubility to fluctuate correspondingly to the mean value. Therefore, the dissolving power during the private period will periodically change between the maximum and minimum values, and the maximum dissolving power available exceeds the average value when there is no ultrasound. Therefore, the overall effectiveness of the dissolution process can be improved without increasing the average operating pressure. Conventional wet-type ultrasonic cleaning uses a temporary liquid cavity effect accompanied by bubble collapse, and the energy generated is released to remove contaminants. This cavitation may damage the fine shapes of the new semiconductor device. The process of the present invention is preferably performed entirely in a thick fluid region so that no phase change occurs and therefore no cavitation occurs. Embodiments of the present invention instead use high-frequency fluid oscillations close to their natural frequency to excite adherent contaminants, 39 1221007 thus being removed. Because there is no cavitation, power loss is reduced and acoustic wave flow is enhanced. [0092] A further embodiment of the present invention is a variable frequency ultrasonic process that uses ultrasonic frequencies to change during processing. Variable frequency ultrasonic processing eliminates static oscillating nodes on the surface of the object being processed and ensures that particles such as particles with a broad natural frequency are removed and suspended in a thick processing fluid. The frequency used in the present invention can range from typical ultrasonic to megahertz (about 20 Kb to 2 MHz). In an embodiment, the variable frequency ultrasonic processing may include: starting cleaning or processing at the lower frequency of the range, and calling for increasing the frequency gradually to the final frequency at the upper level of the range during the cleaning. Alternatively, the variable frequency ultrasonic processing may include: starting cleaning or processing at the upper frequency of the range, and gradually reducing the frequency to the final frequency at the lower frequency of the range. In another alternative, during cleaning or processing, the frequency can be raised and lowered multiple times within this range. [0093] In another embodiment of the present invention, the ultrasonic energy is intermittently input into the process equipment during cleaning or processing. In this embodiment, the switching action of the ultrasonic transmitter will provide intermittent power pulses in the dense phase processing fluid. This pulse will, for example, prevent contamination from being captured by standing waves during cleaning. ^ When the ultrasonic transmitter is turned on, the frequency can be fixed or variable, and during most pulse periods, the frequency can be fixed or variable. [〇 0 9 4] Variable frequency or intermittent ultrasonic treatment can be used with thick fluids containing no processing agent or thick fluids containing one or more processing agents. During the cleaning or treatment step, any combination of frequency or day and / or intermittent treatment periods can be used with the thick fluid or thick treatment fluid. For removing various contaminant particles from cleaning objects, the combination of 变 ^ φ, 贝, and / or intermittent ultrasonic energy with a selected treatment agent in a thick body is particularly useful. [0095] The use of ultrasonic energy is complemented by cleaning and treatment with 々 稠 〇 thick>, because the bathing is effective for smaller soluble ^ A ^ 1, and ultrasonic cleaning or for large branches Or insoluble particulate T? Is effective. Ultrasonic cleaning or processing is instructive for deep patterned surfaces (effective (that is, not sensitive to surface topography), and the method can be used for automation. Ultrasonic carcass cleaning can provide the equivalent of wet chirp cleaning Efficiency, but without the limitation of wet chemical treatment. For example, any method; T method can remove 90% of 0.05 micron particles and larger diameter particles to form a surface density of less than 0.1 particles / cm 2. 0096] Thick fluids or thick processing fluids used with variable frequency and / or intermittent ultrasonic processing can be provided as described with reference to Figure 3. Alternatively, thick fluids used with variable frequency and / or intermittent ultrasonic processing The thick processing fluid can be directly prepared in the processing container. The preparation method is as follows: the subcritical fluid is input into a sealable processing chamber and the processing chamber is isolated, and the subcritical fluid is heated in a substantially fixed volume and a substantially fixed density to generate a thick fluid. And providing a thick processing fluid by one or more steps selected from the group consisting of: (7) subcritical fluid is input into a sealable Before the processing chamber, one or more processing agents are inputted into the sealable processing chamber; (8) After the subcritical fluid is inputted into the sealable processing chamber, but before the subcritical fluid therein is heated, one or more processes are processed. Agent is input into the sealable processing chamber; (9) after the subcritical fluid is input into the sealable processing chamber and after heating 41 1221007 one or more processing agents are inputted into the subcritical fluid therein the sealable processing chamber Medium. [_7] Dense fluid and thick processing fluid are quite suitable for ultrasonic processing. The relatively low viscosity of this fluid minimizes the viscosity loss rate of ultrasonic waves in the fluid. Therefore, the ultrasonic Rotating to the processing table with a slight reduction ^ This allows high process efficiency with minimal chirp losses. Low viscous losses also increase the sonic flow of thick fluids or processing fluids in the cleaning process. Particulates and dissolved contaminants

Removed by rinsing. This will bring fresh solvents near the surface, thereby forming a higher concentration gradient of dissolved contaminants near the surface and increasing the diffusion rate of dissolved contaminants removed from the surface. As a result, the processing time required to form a clean surface is reduced. [0098] The relatively low viscosity of thick fluids also reduces the thickness of the fluid interface layer near the surface. The following equation for the thickness of the sonic interface layer (") shows the tendency towards a thinner sonic interface layer: 5bc = / "

Where is the dynamic viscosity of the fluid, and f is the frequency of the wave. A thinner fluid interface layer causes particles to adhere to the surface to be removed because it is exposed to a larger average fluid viscosity in the thin interface layer (compared to a thicker, lower viscosity interface layer) ). [0099] When the present invention is applied, semiconductor substrates can be individually cleaned or processed by other single-substrate processing modules, providing direct process integration. Alternatively, most substrates or batches of substrates can be cleaned or processed at the same time in a container or "crystal boat" placed in the cleaning or processing chamber, thus providing high productivity and low operation. 42 1221007 This 0 [〇 (Π〇_ Provided is a method for removing insoluble contaminants from the surface. 'The method provided in Ultrasonic Improving Cleaning of Semiconductor Substrates by Ultrasonic Waves by Dense Fluid Immersion Method is provided. The method is to make the tremor m and sound waves flow. And increase the rate of penetration of the thick film pollutant layer by the solvent and co-solvent. Therefore, the required processing time can be shortened. The thickness of the dissolved reactant or the concentration boundary of the pollutant near the surface can be reduced by sonic flow. This will cause the dissolved reactants to diffuse to the surface or soil the surface.

Required processing time. This also reduces the density of the thick processing fluid required to effectively dissolve soluble reactants or contaminants. This will further reduce the force required for the thick processing fluid and reduce the overall success of the processing equipment required to obtain effective processing conditions. This will reduce the number of fluids required to obtain effective processing performance # and reduce Concentrations and quantities of co-agents or reactants required to obtain effective processing performance. Therefore, the overall process cost, chemical waste requirements, energy requirements, and environmental damage caused by the process can be reduced.

[00101] The following examples illustrate embodiments of the invention, but do not limit the embodiment to any specific details described herein. Example 1 [00102] The embodiment of the present invention according to FIG. 3 is used to process a wafer having a photoresist layer with a thick processing fluid described below, wherein the photoresist layer has been subjected to exposure, development, #etching and And / or multiple processing steps such as planting. [0010] Step 1: At ㈣ and 853.5 psiaT, the M container 303 with a volume of 2.71 43 1221007 liters was completely filled with 4.56 lb of saturated liquid carbon dioxide. The initial CO2 carrier density was 47 6 lb / ft3. Seal the container. [00104] Step 2: The pressurized container is heated until the internal pressure reaches 5, just-a. The density of internal carbon dioxide is maintained at 47.6 lb / ft3 and the temperature reaches 189F. Internal carbon dioxide is converted into a thick fluid in the supercritical region (see Figure 1). [00105] Step 3: Load the contaminated silicon wafer in a process equipment 362 with an internal volume of i liters. Evacuate the process equipment and maintain the container wall and wafer at 104 ° F. Step 4: Open the valve 333 that connects the pressurized container 303 to the process equipment 362 via the manifold 331 and the line 361, flow carbon dioxide from the pressurized valleyr 303 into the process equipment 362, and submerge the wafer in Dense phase in carbon dioxide. The temperature of the pressurized container 303 was maintained at 189 ° F. The combined pressure of the pressurized container and the process module is 2,500 psia. The temperature of process injury 362 was maintained at 104 ° F. When 1.79 lbs of carbon dioxide flows into 1 liter of process equipment 362 'and the remaining 2.77 lbs of carbon dioxide still exists in the 2.71 liter pressurized container 3 03, the thick-phase carbon dioxide is still stored in two supercritical states in two Container. The CO2 density in the cooler process equipment is 50.6 lb / ft3. [00107] Step 5: Pump the azeotrope (propylene carbonate) from the azeotrope storage container 353 to the process equipment 362 by the pump 357, and isolate the process equipment. The propylene carbonate concentration in the thick fluid in the process equipment was i% by weight. The thick fluid is stirred in the process equipment 362 for two minutes. During this stirring period, 44 is processed by the following day to remove contaminants. During this period, the ultrasonic transmitter 370 operates at an ultrasonic frequency of 40 KHz, while the high-frequency power supply 371 provides 40 W / in2 ultrasonic power density power. ] Step 6 • When the system pressure is maintained at 900 psia, open the valve 333 ’351, 375, 377, 397, so that the process equipment 362 and the pressurized capacity

The fluid in the separator 303 passes through the cooler 379 and the phase separator, and flows to the carbon dioxide liquefier 341. The azeotrope, reaction products and pollutants are separated from carbon monoxide in a separator 383. During this step, the temperature of the pressurized container 303 was maintained at 189T, and the temperature of the process equipment was maintained at 104T. The carbon dioxide in the two troughs is the vapor phase. Ignoring the rather small effects of the other mixture components, the carbon dioxide density in process equipment 362 is 1032 lb / ft. 0.36 lb of carbon dioxide is still present in process equipment 362. [00109] Step 7: Close the valve 333 to isolate the pressurized container, and cool the internal carbon dioxide generator to 70 ° F, where the pressure drops to 632 psia and the density of the vapor is maintained at 7.07 lb / ft3.

[00110] Step 8: By closing the valve 375 and opening the valve 391, the remaining 0.36 lb of carbon dioxide in the process equipment 362 is exhausted, the equipment is evacuated, and the processed clean silicon wafer is removed. [00111] Filling with liquid carbon dioxide returns the pressurized container 30 to step 丨 and repeats the cycle. Example 2 [00112] The process of Example 1 was repeated, except that during the cleaning in step (5), the operating sonic frequency of the ultrasonic transmitter system 370 started at 20 KHz, and the acoustic wave at the end of the alpha washing was 45 1221007, The frequency cleaning period was increased to 200 KHz at a fixed rate. [00113] The process of Example i was repeated, ^ ^ ^ 55 Q7H 'During the cleaning period of step (5), the ultrasonic wave frequency of the job was sent at a fixed rate during the request period. Increased so that the frequency of the sound wave at the end of 仵 / month 为 is 20 KHz 〇 [〇〇114] Repeat the process of Example 1 except that during the cleaning of step ，, the ultrasonic transmitter 37G is turned on The transmitter system works intermittently with i seconds and off i seconds. The sound wave frequency during the start of the transmitter system is 40 KHz. Brief description of the drawings [0 031] The first diagram is the density-temperature phase diagram of carbon dioxide. [0 032] Figure 2 is a general density-temperature phase diagram. [0 033] FIG. 3 is a process flowchart of an embodiment of the present invention. [0034] FIG. 4 is a schematic view of a pressurized container used in the embodiment of FIG. 3. The drawing numbers of the main components are: 1 saturated liquid curve; 3 saturated vapor curve; 5 critical points; 7 dissolution curve; 201 saturated liquid curve; 203 saturated vapor curve; 205 critical point; 207 46 1221007 critical isobar; 209 single phase super Critical fluid zone; 211 single-phase compressed liquid zone; 301 carbon dioxide supply container; 303, 305, 309 pressurized container; 311, 331 manifold; 313, 315, 317 pipeline; 319, 321, 323, 333, 335, 337 valves 325,327,329 fluid supply lines; 339 bidirectional flow tubes; 341 carbon dioxide liquefiers; 343 heat exchangers; 345, 347, 349 pressure sensors; 351 metering valves; 353, 355 azeotrope storage containers; 357, 359 372 pumps; 361 pipelines; 362 process equipment; 363 objects; 365 carriers; 367 temperature control systems; 369 fluid stirring systems; 370 ultrasonic generators; 371 high-frequency power supplies; 373 filters; 375, 377 valves; 379 cooling 381 pipeline; 383 separator; 387 pipeline; 389 intermediate fluid storage container; 391 valve; 393 filter system; 395, 397, 398 pipeline; 399 valve; 401 outer pressure envelope; 403 inner container; 405 thermal insulator 407 opening 409 differential pressure sensor; 411,413,415 pipeline; 417 liquid; 419 vapor; 420 pipeline; 4 21 heating fluid; 4 2 3 pipeline; 4 2 5 heat exchanger; 4 2 7 pipeline; 429 heat sink; 431 tube body

47

Claims (1)

l22l〇07 Patent scope of inspection and application: 1'A method for processing an object, the method includes: ('Enter the object into a sealable processing chamber, and seal the processing chamber .... Fluid: (bl) input a subcritical fluid into a pressurized container and isolate the container; and ㈣, (b2) heat the subcritical fluid under a substantially fixed volume and a substantially fixed density to produce a dense fluid; (C) Conveying at least a part of the thick fluid from the pressurized container to the processing chamber, wherein the conveying of the thick fluid is driven by the pressure difference between the pressurized container and the processing chamber, thereby using the delivered thick fluid Pressurize the processing chamber; (d) input one or more processing agents into the processing chamber before (C) or during (c) or after (c) to provide a thick processing fluid; (e) apply Ultrasonic energy is input into the processing chamber, and the object is brought into contact with the thick processing fluid, resulting in waste thick processing fluid and the processed object; and (f) separating the waste thick processing fluid from the processed object 2 · If the scope of patent application A method according to item 1, wherein the thick fluid in (b2) is produced in the pressurized container at a contrast temperature lower than about 1.8, wherein the contrast temperature is defined as the average absolute value of the thick fluid in the pressurized container after heating. The temperature is divided by the absolute critical temperature of the fluid. 48 1221007 3. As in the method of claim 2 of the patent application, in (d), the contrast temperature between about 0.8 and about 1.8 can be used in the processing chamber to make the The object comes into contact with the thick processing fluid in the processing chamber, wherein the comparative temperature is defined as the average absolute temperature of the thick processing fluid in the processing chamber during (d) divided by the absolute critical temperature of the thick processing fluid. For example, the method of claim 1, wherein the thick fluid contains one or more components selected from the group consisting of: stone dioxide, nitrogen, methane, oxygen, ozone, argon, hydrogen, helium, Ammonia, Nitric Oxide, Fluoride_Hydrogen Chloride, Hydrogen Chloride, Sulfur Trioxide, Sulfur Hexafluoride, Nitrogen Trifluoride, Monofluoromethane, Monofluoromethane, Ermobi, Ermobi, Tetrafluoroethyl , Pentafluoroethane, perfluoropropane, pentafluoro Propane, hexafluoroethane, hexafluoropropylene, hexafluorobutadiene and octafluorocyclobutane and tetrafluoroethane. 5. The method according to item 1 of the patent application scope, wherein the thick fluid comprises One or more hydrocarbons that interfere with the atom. 6. The method of claim 1 in which the total concentration of one or more treatment agents in the thick treatment fluid may be between about 0.1 and 20% by weight. 7. The method according to item 1 of the patent application scope, wherein the thick treatment fluid comprises one or more treatment agents selected from the group consisting of ethyl acetate, ethyl lactate, propyl acetate, butyl acetate, Diethyl ether, dipropyl ether, methanol, ethanol, isopropanol, acetonitrile, propionitrile, benzonitrile, cyanoethanol, 49 1221007 monoalcohol monoacetate, acetone, tripropylamine, tributyl, dibutyl ether Ethylethanolamine, diethylene glycol, propylene glycol, ethylene glycol acetate, propyl ethyl ketone, acetophenone, trifluoroacetophenone, triethylamineamine, 2,4-difyl nitrogen benzene, dimethylethanolamine Methyl amine, dimethyl methanol amine, dimethyl formamidine — Hey-T-Acetomethamine Ethyl Alcohol% i Acid S purpose, propylene carbonate purpose, acetic acid, lactic acid, butanol-propanol, n-hexane, N-butane, hydrogen peroxide, third butyl hydrogen peroxide, ethylenediaminetetraacetic acid, catechol, choline and trifluoroacetate. 8. The method according to item 1 of the patent application scope, wherein the thick treatment fluid comprises one or more treatment agents selected from the group consisting of hydrogen fluoride, hydrogen gas, hydrogen trifluoride, and nitrogen trifluoride , Monofluoromethane, difluoromethane, trifluoromethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, perfluoropropane, pentafluoropropane, hexafluoroethane, hexafluoropropylene, hexafluoro Butadiene, octafluorocyclobutane, tetrafluoroethane, fluorotrifluoromethane (CF4〇), bis (difluorooxy) methane (CF4〇2), melamine fluoride (c3F3N3), ethyl Difluoride difluoride (c2F2N2), nitrosium fluoride (CFO), carbon fluoride (cf20) and perfluoroamidine (cf5N). 9. The method of claim 1, wherein the thick processing fluid comprises one or more processing agents selected from the group consisting of: organometallic preform, photoresist, photoresist developer, intermediate Layer dielectric material, Shixijing reagent and antifouling coating. 0 · The method according to item 1 of the scope of patent application, further comprising reducing the pressure of the waste thick treatment fluid to generate at least one fluid phase and a residual compound 50 1221007 phase, and the phase can be separated to produce a purified fluid and a recovery residue Compounds. 11. The method of claim 10 in the scope of patent application further comprises recycling purified fluid 'to provide a portion of the subcritical fluid in (b 1). 12. The method according to item 10 of the scope of patent application, further comprising reducing the pressure of the purified fluid to generate a further purified fluid phase and a new residual compound phase, and the phase can be separated to produce a further purified fluid. With new recovered residual compounds. 13. According to the method of the patent application, ^ ^ ^ guide the method, and further includes recirculating the further purified fluid to add eight ^ t 乂 & part of the subcritical fluid in (bl) . The method of item (1), wherein the heated subcritical fluid of (b2) includes a vapor phase and a liquid phase. As before the scope of patent application No. 1, the or coexisting vapor and liquid phase in the pressurized container. 15. · A method for processing a material, which includes: (a) inputting the object into a sealed processing chamber, and sealing the processing chamber 3; preparing a thick processing fluid by: The human critical fluid is input into a pressurized container, and the container is separated, and the container is heated at a substantially fixed volume and a substantially fixed density to produce a dense fluid; & 51 1221007 (b3) under the following conditions Enter one or more treating agents into the pressurized container: before the subcritical fluid is input into the pressurized container 'or after the subcritical fluid is input into the pressurized container' but after heating the pressurized container Before, or after inputting the subcritical fluid into the pressurized container 'and after heating the pressurized container; (c) transferring at least a portion of the thick processing fluid from the pressurized container to the processing chamber, wherein the The transport of the thick processing fluid is driven by the pressure difference between the pressurized container and the processing chamber, thereby pressurizing the processing chamber with the thick processing fluid being transported; (d) inputting ultrasonic energy into the processing chamber in, Contacting the object with the transported thick processing fluid to produce a waste thick processing fluid and the processed object; and (e) separating the waste thick processing fluid from the processed object. 16. A method for processing Article of equipment comprising: (a) a fluid storage tank containing a subcritical fluid; (b) one or more pressurized containers and conduit mechanisms for transferring the subcritical fluid from the fluid storage tank To one or more pressurized containers; (c) a heating mechanism for heating the contents of each of the one or more pressurized containers at a substantially fixed volume and a substantially fixed density to convert the subcritical fluid into Thick fluid; (d) a sealable processing chamber for contacting an object with the thick fluid; 52 1221007 (e) an ultrasonic generation mechanism for inputting ultrasonic energy into the sealable processing chamber; ( f) a conduit mechanism for transferring the thick fluid from the one or more pressurized containers into the sealable processing chamber; and (g) one or more treatment agent storage containers and pressurization mechanisms to Used to combine one or more processes Injection into (1) the one or more pressurized containers' or (2) the conduit mechanism for conveying the thick fluid from the one or more pressurized containers to the sealable processing chamber, or (㈧ the Can be sealed in the processing chamber. 17. If the device in the scope of patent application No. 16 further includes a pressure reducing mechanism and a phase separation mechanism 'to separate the waste carcass extracted from the processing chamber, and generate to J -A purification fluid and one or more recovered residual compounds. 18. The device of claim 17 in the patent scope further includes a circulation mechanism for circulating the purification fluid to the fluid storage tank. 19. A method for processing an object, the method comprising: feeding the object into a sealable processing chamber, and providing a thick processing fluid to the processing " When the fluid is in contact with the ultrasonic energy, the frequency of the ultrasonic energy is changed and the waste thick processing fluid is produced from the treated object; and the waste thick treatment fluid is separated from the treated object. 53 1221007 During the period of 20, the method of applying for patent scope 帛 19, where the frequency of ultrasound energy can be increased. 21. The method of applying for scope 19 of patent application, where the ultrasonic energy can be reduced. Frequency 22. The method according to item 19 of the scope of patent application, wherein it is prepared in the following manner: The thick processing fluid can be &) input a subcritical fluid into a pressurized container, and separate the container; (b) heating the subcritical fluid 'at a substantially fixed volume and a substantially fixed density to produce a thick fluid; and (c) providing the thick treatment fluid by one or more steps selected from the group consisting of ·· (1) When the temple fluid is delivered from the pressurized container to the processing chamber, one or more processing agents are input into the thick fluid; (2) One or more processing agents are input into the pressurized container to form a thick Process fluid and transfer the thick process fluid from the pressurized container to the processing chamber, (3) after the thick fluid is transported from the pressurized container to the processing chamber, 'input one or more processing agents into the process Into the thick fluid in the cavity; 54 (4) before the subcritical fluid is input into the pressurized container, one or more treatment agents are input into the pressurized container; (5) before the subcritical fluid is input into the pressurized container After pressing the container, but before heating the pressurized container, one or more treating agents are input into the pressurized container; (6) After the subcritical fluid is input into the pressurized container, and after the pressurized container is heated , One or more processing agents to enter the pressurized container. OQ • The method according to item 19 of the scope of patent application, wherein the thick processing fluid can be prepared by: (a) entering a subcritical fluid into the sealable processing chamber and isolating the processing chamber; (b) in essence Heating the subcritical fluid at a fixed volume and a substantially fixed density to produce a thick fluid; and (c) providing the thick processing fluid by one or more steps selected from the group consisting of: (1) in Before the secondary fluid is input into the sealable processing chamber, one or more processing agents are input into the sealable processing chamber; (2) After the subcritical fluid is input into the sealable processing chamber, but Before heating the subcritical fluid therein, one or more treating agents are input into the sealable 55 1221007 processing chamber; and (3) after the subcritical fluid is input into the sealable processing chamber, and after heating After this subcritical fluid, one or more processing agents are input into the sealable processing chamber. 24 · —A method for processing an object, the method comprising: (a) entering the object into a sealable processing chamber, and sealing the processing chamber; (b) supplying a fluid to the processing chamber; ( c) when the object is in contact with the thick fluid, the ultrasonic energy is input into the processing cavity, and the frequency of the ultrasonic energy is changed to generate waste thick fluid and the processed object; and (d) the waste thick The fluid is separated from the treated object. 25. A method for processing an object, the method comprising: () entering the object into a sealable processing chamber, and sealing the processing chamber; (b) providing a thick processing fluid in the processing chamber; (C) Although the object is in contact with the thick processing fluid, the ultrasonic energy is intermittently input into the processing chamber to generate waste thick processing fluid and the processed object; and ⑷ separating the waste thick processing fluid from the processed object . 26 · —A method for processing an object, the method comprising: (a) sealing the object into a processing chamber; sealing the processing chamber; and providing a thick fluid at the processing site 56 1221007 (b) (C) when the object is in contact with the thick fluid, ultrasonic energy is intermittently input into the processing cavity to generate waste thick fluid and the processed object; and the waste thick fluid and the processed object Objects are separated. 57